Method of making beta-pinene and vinyl cyclohexene resin



Patented Sept. 18, 1951 UNITED STATE METHOD OF MAKING BETA-PINENE ANDVINYL CYCLOHEXENE RESIN Samuel G. Burroughs, Pittsburgh, Pa., asaignorto Pennsylvania Industrial Chemical Corporation, Clair-ton, Pa., acorporation of Pennsylvauia No Drawing.

This invention relates to a resin composed of mixed vinyl cyclohexeneand beta-pinene polymers and/or copolymers.

l-vinyl cyclohexene-3 is produced as a derivative of cyclohexene formedas a by-product in certain catalytic processes, such as processes ofmaking butadiene. As produced it is associated with cyclohexanol andrelated alcohols in a combined proportion of about to of thosesubstances. This impure, approximately 85% vinyl cyclohexene'polymerizesunder the influence of aluminum chloride and related acidreacting metalhalide catalysts very slowly and incompletely to form two types ofresin, one of which has a melting point of about 100 and is soluble inmineral spirits at normal room temperature, and the other of which isinfusible and is insoluble in all commonly used or anic solvents. Thesetwo types of resin are formed approximately simultaneously and separatefrom each other with precipitation of the insoluble type. Because ofpoor yield and the impossibility of directing the polymerizationreaction, the impure cyclohexene is to be considered valueless as astarting material for the production of resin of either type. I have,however, found that by purifying the vinyl cyclohexene and by subjectingit to polymerization in association with betapinene, I am able to obtaingood yields of solid resins Any suitable purification procedure may befollowed to obtain an approximately pure vinyl cyclohexene startingmaterial. One specific procedure which I have advantageously followed isto wash the impure vinyl cyclohexene by-product with 59 Baum sulphuricacid (74%) at 5 C. The product of the purification consists at leastabout 95% of pure vinyl cyclohexene responding apparently to the formulaEL i This acid washed vinyl cyclohexene has a specific gravity of 0.8336at 15.5 C.. a boiling range of 125 C. to 131 C., a bromine number of280, and a refractive index of 1.464 at C. This material when dilutedwith a hydrocarbon diluent,

Application August 23, 1943, Serial No. 45,786

7 Claims. (Cl. 260-881) such as toluol, and subjected to apolymerization reaction with aluminum chloride. or its substantialequivalent as a catalyst, gives a. yield of about of iniusible insolubleresin, and about a 20% yield of resin having a melting point of 80 0.(ball and ring) which is soluble in mineral spirits at normal roomtemperature. There is great diversity in the properties of the diversetypes of resin so produced inasmuch as the insoluble type is not solubleto any appreciable extent in toluol, acetone, alcohol, ethyl-acetate,carbon tetrachloride. or mineral spirits. with heating. It also is notsoluble in molten coumaronc-indene resin, or molten terpene resin. -Theinsoluble type of vinyl cyclohexene resin does not melt up to itsdecomposition point. A less carefully acid washed vinyl cyclohexene,which I also have used, is between and pure.

Whereas the two diverse resins of the insoluble and soluble types haveeach its individual utility. I have discovered that a more usefulproduct is obtained by polymerizing a mixture of the vinyl cyclohexene,which as shown in the formula is a mixed cyclic and open chain material.with beta-pinene to produce a soluble, thermoplastic resin. Apparentlysuch resin is in part at least the result of copolymerization, inasmuchas up to a certain percentage of the vinyl cyclohexene only solublepolymers are formed.

Beta-pinene is a turpentine constituent giving a peculiarly highresponse to polymerization promoting stimuli, and particularly topolymerization with the acid-reacting metallic halides. It is present insubstantial proportion in gum spirits of turpentine derived by tappinlive conifers and by distillation of the liquids thus obtained, beingpresent in that turpentine in a proportion of about 30% thereof. It alsois present in a proportion of about 25% of the whole in sulphateturpentine which is a liquid extracted from the waste produced in theprocess of making sulphate pulp from the wood of conifers. Ascommercially available from either of these sources the betapinene whichis sold as such is about 85% to 95% pure, varying with the methods usedin its separation from the associated mono-cyclic and bycyclic terpenes.It boils close to 165 C. and has an aniline point by the standardmethods of aniline point determination of about.34 0.

As polymerized by itself by brin n it into reactive contact withaluminum chloride or an equivalent acid-reacting halide, the commercialbeta-pinene, about 85% pure, gives an approximately 85% yield of terpeneresin having a softening point (ball and ring) of from about c. to 1200. when brought to a state of approximate purity, the beta-pinene givesan approximately 100% yield of terpene resin having a softening point(ball and ring) of about 130 C. to 135 C. By mixing beta-pinene, ineither an impure commercial exempliflcation of that material or a plantprepared beta-pinene over 95% pure, with vinyl cyclohexene, a yield ofhigher melting point resin than is obtainable from beta-pinene by itselfis obtained in a yield at least equal to that obtained without inclusionof the vinyl cyclohexene. In mixtures of vinyl cyclohexene withbeta-pinene below the maximum permissible proportion of the vinylcyclohexene, approximately all of the vinyl cyclohexene which isincluded partakes in the formation of soluble thermoplastic resinwithout any substantial formation of insoluble polymers.

As a general procedure the vinyl cyclohexene which has been subjected toa purification treatment is mixed with the beta-pinene and with anorganic diluent which is substantially inert to polymerization with thevinyl cyclohexene and the terpene, and is brought into reactive contactwith an acid-reacting metal halide polymerization catalyst, such asanhydrous aluminum chloride, aluminum bromide, stannic chloride,titanium tetrachloride, antimony pentachloride, ferric chloride and thecorresponding bromides of these latter metals, aluminum chloride andaluminum bromide being preferred. During the progress of thepolymerization reaction. the reaction temperature is maintained within arange which desirably is suitable for relatively rapid polymerlzationwithout reaction surge, such as a temperature within the approximaterange of C. to 80 C., a temperature within the range of about 35 C. to60 C. being considered optimum from the viewpoints of reaction speed andease of temperature control. Upon the completion of catalyst addition,which desirably is effected without such rapidity as to cause a surge,agitation of the reaction mixture is continued for a substantial periodof time completely to polymerize theyinyl cyclohexene which appears tolag in the combined polymerization reaction.

To remove the catalyst at the end of the polymerization treatment twostandard recovery methods may be employed. In accordance with one suchprocedure the mixture is drowned with a water solution of hydrochloricor sulphuric acid, and is then water washed and neutralized with a watersolution of sodium carbonate. The washed solution is then warmed to 60C. and is allowed to settle until a clear resin solution is obtained.Such resin solution is distilled, desirably at a still temperature ofabout 210 C., and is then steam distilled at still temperatures withinthe range of about 210 C. to 260 C. until a resin of the desiredsoftening point remains as a residue.

The other method of removing catalyst and recovering solid resin tendsto give a somewhat lighter color than the method described above. Inaccordance with this latter procedure the polymerization mixture isallowed to settle until the metal halide sludge separates out, whichseparation is complete within about one hour to twenty-four hours. Thesolution is decanted off, the sludge is washed with a suitable organicsolvent, such as refined solvent naphtha, and the washings are added tothe resin solution. The combined resin solution thus obtained is clear,but is deep red in color due to the retention of a soluble complex ofthe metal halide.

4 This clear but highly colored solution is purified by refluxing it ata still temperature of about C. to C. with fullers earth having butslight acidity, which is not of necessity dry, and slaked lime for aperiod of three hours. During this treatment hydrochloric acid is drivenoff and the original soluble aluminum chloride complex comes down as aprecipitate. An appropriate quantity of clay for use in the refluxpurification is about 7.5% of the total weight of vinyl cyclohexene andbeta-pinene and a quantity of lime equal to the weight of the claydesirably is used. As low as 5% clay and lime may be used and as muchmay be used as will not interfere with the refluxing. Up to as much as15% to 20% each of clay and lime is usable. After refluxing, the resinsolution is filtered and a clear light yellow resin solution isobtained, one of the common commercial filter aids desirably being usedduring the filtering. This resin solution is then steam distilled,desirably at still temperatures of about 210 C. to 260 C., until solidresin of the desired melting point remains as a residue.

The above recovery procedure results in the production of a resin ofparticularly light color. but does so at the sacrifice of a smallproportion of the resin yield which is retained in the sludge initiallyseparated from the resin solution. This proportion of the resin carrieddown with the sludge may largely be recovered by drowning the sludgewith a 5% water solution of hydrochloric acid or sulphuric acid, thenagitating the resin with an organic solvent, such as distilled solventnaphtha, and distilling off the solvent. This leads to recovery ofentrapped resin which is of darker color than that obtained by steamdistillation of the resin solution.

It has been noted that the mixture of vinyl cyclohexene and beta-pineneis diluted with an organic solvent diluent inert to polymerization underconditions of the process. That diluent preferably is one of the lowaniline point organic solvents which is inert in the process, as forexample one of the aromatic hydrocarbon solvents which have nounsaturation outside the benzene ring, such as benzol, toluol, xylol,refined solvent naphtha and ethyl benzene. or one of the chlorinatedaromatic solvents, such as chlorobenzol. Regardless of the specificsolvent which is used, most desirably it is included in a quantity notsubstantially less than 30% the total reaction liquid in order tomaintain activity as polymer formation proceeds. It can be included inany greater quantity subject to the practical consideration thatincreased volume of diluent tends to slow the reaction and to increasethe reaction time, and also to require that an increased quantity ofcatalyst be used in order to make reactive contact with thepolymerizable vinyl cyclohexene and beta-pinene. Also it is uneconomicalto use and distill off more diluent than performs a useful purposeduring the polymerization reaction. As a practical consideration Iprefer to include the diluent in no more than about 80% of the totalvolume of the reaction mixture.

I have found that in using anhydrous aluminum chloride or aluminumbromide as the polymerization catalyst as little as 1% by weight of suchcatalyst with respect to the combined weight of the vinyl cyclohexeneand beta-pinene is sufficient to effect complete polymerization, andeven less than 1% may usefully be employed. Preferably I utilizeanhydrous aluminum chloride or aluminum bromide in a quantity equal toabout 3% to 15% the weight of the combined vinyl cyclohexene andbeta-pinene in accordance with the other conditions of the process.Quantities of those catalysts over 25% eflect no appreciable shorteningin the time required for the polymerization reaction even when conductof the polymerization at low temperature indicates the use of arelatively large proportion of catalyst, unless a particularly greatvolume of diluent also be used. In proportioning the catalyst to thepolymerizable constituents of a reaction mixture the other metal halidecatalysts of the Friedel-Crafts type which have been noted above canusefully be proportioned to the above preferred quantities of anhydrousaluminum chloride and aluminum bromide. In substituting aluminum bromideand the other metal halide catalysts for the aluminum chloride, theoptimum proportion of catalyst to the polymerizable content of thereaction mixture is desirably increased or decreased with respect to thequantity of aluminum chloride used in proportion as the molecular weightof that particular catalyst is greater or less than that of aluminumchloride.

It has been noted above that in subjecting a mixture of vinylcyclohexene and beta-pinene to polymerization the vinyl cyclohexenefunctions in the mixture to raise the melting point of the resin whichmay be recovered. It is to be noted that this function is performed downto the least proportion of vinyl cyclohexene which gives a perceptibleincrease. That minimum proportion is, as will be exemplified herein,below of vinyl cyclohexene in the mixture of that material withbeta-pinene, if in fact there is any proportion which may be consideredas an absolute minimum exerting no-measurable effect on the productresin. For purposes of practical definition of the point at which theefiect of including vinyl cyclohexene becomes negligible, I give 5% as aminimum. In seeking to obtain resin of particularly high melting pointthe proportion of vinyl cyclohexene to beta-pinene can be increased forthe production of high melting thermoplastic resin up to a point atwhich the proportion of insoluble polymers renders further increase inthe proportion of the vinyl cyclohexene uneconomical. I have found thatthe best average results both as to the melting point of thethermoplastic resin which is produced and the yield of suchthermoplastic resin are obtained when the vinyl cyclohexene constitutesabout 25% to 45% of the polymerizable mixture, there being a substantialproduction of insoluble resin when equality in the weights of the twoingredients is approached with rapid increase above that point.

My starting material for polymerization thus comprises a mixture ofbeta-pinene and vinyl cyclohexene in which the vinyl cyclohexene isincluded in a proportion of from 5% to 50% of the total blend and mostdesirably in a proportion of from 25% to 45% of the blend in order toobtain maximum inclusion of vinyl cyclohexene in the resin polymerswithout forming insoluble polymers, the proportions being by weight.This proportioning includes those blends in which the beta-pinene isfrom 85% to 95% pure as well as those in which the beta-pinene is from95% to 100% pure.

The following will exemplify the method of my invention.

Example 1 In this example the vinyl cyclohexene forming an element ofthe blended starting material was about 95% pure figured on the basis oftotal unsaturation in accordance with a bromine number of 280. Thebeta-pinene was approximately pure, and distilled over within the rangeof 160 C. to 166 C. (vapor temperature). The vinyl cyclohexene had beenpretreated with 59 Baum sulphuric acid neutralized and washed withwater. The beta-pinene when subjected to polymerization by itself underthe influence of anhydrous aluminum chloride gave an 85% yield of C.(ball and ring) softening point terpene resin. The reaction mixture wasmade up by blending 140 cc. (116 gm.) of vinyl cyclohexene and 140 cc.(120 gm.) of the beta-pinene with 300 cc. of toluol. 18 gm. of anhydrousaluminum chloride was added as catalyst and was brought with agitationinto reactive contact with the vinyl cyclohexene and beta-pinene of thereaction liquid. The catalyst was added to the reaction mixture in smallincrements during a period of 1 hour and after addition of the catalystwas complete the reaction mixture was stirred for an additional periodof 2 hours. During the reaction the temperature was held by circulationof heat abstracting liquid through cooling jackets to a range of 35 C.to 45 C. Insoluble resin in the amount of 16 gm. was formed.

At the end of the polymerization treatment the reaction mixture waswarmed to 60 C., was allowed to settle and a clear solution was decantedaway from the sludge. That sludge was drowned with a 5% water solutionof hydrochloric acid and was agitated with distilled solvent naphtha.The solution from the sludge was added to the original solution. Thisentire resin solution was refluxed with clay and lime and was filtered.The filtered solution was distilled to 210 C. (still temperature) andwas steam distilled at a still temperature of from 210 C. to 260 C.until a residue of solid resin was ob-- tained.

The resin recovered by distillation was 200 gm. of thermoplastic solubleresin having a softening point of C. (ball and ring) and a color 6 onthe Gardner scale. This latter resin when dissolved in an equalproportion by weight of mineral spirits showed no cloud down to atemperature of 0' C.

It may be noted that the foregoing example exemplifies the approximatemaximum proportion of vinyl cyclohexene which desirably can be includedin producing a thermoplastic resin from a mixed starting materialconsisting of betapinene and vinyl cyclohexene.

Example 2 In this example the vinyl cyclohexene was acid washed andabout 90% pure and the beta-pinene was of the same grade as inExample 1. They were blended in the proportion of 100 cc. (83 gm.) ofvinyl cyclohexene and cc. (120 gm.) of beta-pinene. This reactive blendwas mixed with 300 cc. of toluol to form the reaction mixture. To thisreaction liquid 18 gm. of anhydrous aluminum chloride was added ascatalyst and was brought with agitation into reactive contact with thevinyl cyclohexene and beta-pinene of the reaction liquid. As in theforegoing example, the aluminum chloride was added to the reactionmixture in small increments during a period of 1 hour. and afteraddition of the catalyst was complete the reaction mixture was stirredfor an additional period of 2 hours. During the reaction the temperaturewas held by circulation of heat abstracting liquid through coolingjackets to a range of 35 C. to 45 C.

The recovery procedure was identical with that of Example 1.

The resin recovered by distillation was a thermoplastic soluble resinhaving a softening point of 157 (ball and ring) and a color on theGardner scale. The yield was 185 gm. (92%) of resin which when dissolvedin an equal proportion by weight of mineral spirits showed no cloud downto a temperature of 0 C. No insoluble resinwas formed.

Example 3 A starting material was-made by mixing vinyl cyclohexene andbeta-pinene of the same grades used in Example 1. The mixture was madeup to include 24 cc. (21 gm.) of the vinyl cyclohexene and 215 cc. (182gm.) of the beta-pinene. This liquid was mixed with 300 cc. of toluol.3% of anhydrous aluminum chloride was added during a period of 1 hourand was brought with agitation into reactive contact with the vinylcyclohexene and beta-pinene of the reaction liquid. The reaction mixturewas stirred for an additional period of 2 hours. During the reaction thetemperature was held within the range of 40 C. to 45 C.

The recovery procedure was identical with that of Example 1.

The resin recovered by distillation was a thermoplastic soluble resinhaving a softening point (ball and ring) of 129 C. and a color 8 on theGardner scale. The Yield of solid thermoplastic resin, no insolubleresin being formed, was 1'79 gm. (88.2%) the weight of the combinedvinyl cyclohexene and beta-pinene. The resin when dissolved in an equalproportion by weight of mineral spirits showed no cloud down to atemperature of 0 C.

The foregoing exemplifies the fact that a relatively small proportion ofvinyl cyclohexene when blended with bata-pinehe materially affects theresults of the polymerization. Thus beta-pinene from the same batch wassubjected to polymerization under identical conditions and the resultwas to obtain an 85% yield of resin having a softening point (ball andring) of 120 C. The color of the resin was 3 on the Gardner scale. Theresult of including with the beta-pinene only a small proportion of thevinyl cyclohexene is therefore to obtain an appreciably increased yieldof a resin or appreciably higher softening point with respect to theyield and softening point obtained by polymerizing the beta-pinenealone.

Example 4 Inthis example vinyl cyclohexene and betapinene of the samegrades as those used in Examples 1 and 3 were mixed. The reactionmixture was made up by mixing 140 cc. (116 gm.) of vinyl cyclohexene and140 cc. (120 gm.) of the beta-pinene with 300 cc. of toluol and 23 gm.aluminum chloride was added as the catalyst and was brought withagitation into reactive contact with the vinyl cyclohexene andbetapinene of the reaction liquid. The catalyst was added to thereaction mixture in small increments during a period of 1 hour and afteraddition of the catalyst was completed the reaction mixture was stirredfor an additional period of 6 hours. During the reaction the temperaturewas held by circulation of heat abstracting liquid through coolingjackets to a range of C. to C. Insoluble resin in the amount of 18 gm.was formed.

At the end of the polymerization treatment the reaction mixture waswarmed to 60 C., was allowed to settle and a clear solution wasdecanted.

Because of the lower temperature at which the polymerization wasconducted there was a greater precipitation of sludge than resulted fromthe polymerization in Examples 1, 2 and 3. This sludge was drowned witha 5% water solution of hydrochloric acid and was agitated with distilledsolvent naphtha. The solution from the sludge was added to the originaldecanted solution.

The entire resin solution was refluxed with clay and lime, was filteredand the filtered solution was distilled at a still temperature of 210 C.and was steam distilled at a temperature of from 210 C. to 260 C. untila residue of solid resin was obtained. The recovery thus was identicalwith that of Example 1.

The resin recovered by distillation was obtained in a total yield of 214gm. (90%) of thermoplastic soluble resin having a softening point of 142C. (ball and ring) and was color 6 on the Gardner scale. This latterresin when dissolved in an equal proportion by weight of mineral spiritsshowed no cloud down to a temperature of 0 C.

Example 5 Vinyl cyclohexene and beta-pinene of the same grade as inExample 2 were mixed in the proportion of 100 cc. (83 gm.) of vinylcyclohexene and 140 cc. 120 gm.) of beta-pinene and were mixed with 300cc. of toluol to form the reaction mixture. To this reaction liquid 20gm. (10%) of anhydrous aluminum chloride was' added as the catalyst andwas brought with agitation into reactive contact with the vinylcyclohexene and beta-pinene of the reaction liquid.

The polymerization procedure and recovery procedure were identical withthat of Example 4.

The resin recovered by distillation was a thermoplastic soluble resinhaving a softening point of 163 C. (ball and ring) and a color 5 on theGardner scale. The yield was 180 gm. (88%) of resin which when dissolvedin an equal proportion by weight of mineral spirits showed no cloud downto a temperature of 0 C. No insoluble resin was formed.

Example 6 Vinyl cyclohexene and beta-pinene of the same grade as inExamples 1, 3 and 4 were mixed in the proportion of 24 cc. (21 gm.) ofvinyl cyclohexene and 215 cc. (182 gm.) of beta-pinene and were mixedwith 300 cc. of toluol to form the reaction mixture. To this reactionliquid 12 gm. (6%) of anhydrous aluminum chloride was added as thecatalyst and was brought with agitation into reactive contact with thevinyl cyclohexene and beta-pinene of the reaction liquid.

The polymerization procedure was identical with that described inExample 4. Because of the relatively great proportion of beta-pineneincluded in the reaction liquid the precipitation of sludge was lessthan in Examples 4 and 5. No insoluble resin was formed.

The recovery procedure was identical with that of Example 1.

The resin recovered by distillation was a thermoplastic soluble resinhaving a softening point of 133 C. (ball and ring) and was color 5 "onthe Gardner scale. The yield of solid thermoplastic resin, no insolubleresin being formed, was gm. (83%) the weight of the combined vinylcyclohexene and beta-pinene. The resin when 15 dissolved in an equalproportion by weight of 9 mineral spirits showed no cloud down to atemperature of C.

The foregoing Examples 4, and 6 illustrate the fact that with lowerreaction temperature it is desirable to use an increased quantity ofcata lyst and to continue the polymerization period for an extendedlength of time in order to secure results close to those obtained athigher temperature. As noted above the vinyl cyclohexene is relativelysluggish in its response to polymerization promoting stimula. It will benoted that in Examples 4, 5 and 6 in which respectively theproportioning of vinyl cyclohexene and betapinene is identical with thatof Examples 1, 2 and 3 the lower temperature of polymerization gives aresin of somewhat higher softening point, obtained in slightly decreasedyield. At the expense of an even more extended reaction period thepolymerization at the lower temperature gives an almost equal yield ofresin as compared with the higher temperature, while obtaining thebenefit of higher softening point.

Using the same proportions of vinyl cyclohexene and beta-pinene as inExamples 1, 2 and 3 polymerization was conducted at a temperature withinthe range of C. to C. In each instance catalyst in a quantity equal to14% the weight of the combined vinyl cyclohexene and beta-pinene wasusedand the polymerization period after addition of the catalyst wasextended to 12 hours. The result was to obtain yields approximatelyidentical with those of Examples 4, 5 and 6 with an increase of about 4C. in the softening point of the resin.

Duplication of the procedures given above but using aluminum bromideinstead of aluminum chloride as catalyst gave almost identical results.The other acid-reacting metal halides are usable in the process. Evenwhen employed in increased quantity they give lower yields of resin.

In all the foregoing examples the beta-pinene' is a commercial, 85%pure, terpene which was not subjected to special purifying treatment. Byusing a beta-pinene which had been brought to over 95% purity, I obtaina yield which in each instance is from 2% to 4% greater and a softeningpoint about 4 C. to 5 C. higher.

The resin produced from a mixed vinyl cyclohexene and beta-pinenestarting material corresponds in most particulars to terpene resins andmore particularly to beta-pinene resin. In all proportioning of the twoingredients of the starting material the resin is usable in all ways inwhich a straight terpene resin is usable, as for example in coatingcompositions, hot melt coatings, adhesives, rubber compounding, chewinggum bases and the like. Guides to satisfactory procedure in such usesare found in patents to Frank W. Corkery and Samuel G. Burroughs No.2,320,717; No. 2,319,389; No. 2,320,716; No. 2,320,- 718; and No.2,357,811.

For some uses the resin of this invention is more advantageous thanbeta-pinene resin and the other terpene resins, because of its somewhathigher softening point. Although terpene resins as carefully produced,are considered to possess good color stability, the resin produced bypolymerizing a mixture of vinyl cyclohexene and beta-pinene exhibitshigher resistance to color development than do the other terpene resins,including straight beta-pinene resin.

It has been noted above that it is desirable in the process to use aninert solvent diluent of low aniline point. I have found it preferableto use such solvent diluents as have an A, S. T. M.

10 D 611-46 T aniline point no higher than 35 C. Most of thecommercially desirable solvents of this sort have aniline points by theabove determination falling within the range of about 15 C. to 35 C.

Throughout the specification aniline point," where not specificallyqualified by the method 0! -its determination, is to be understood asdetermined by the A. S. T. M. D 611-46 T aniline point method. Where notspecifically qualified in the specification, softening point" i to beunderstood as determined by the ball and ring method of softening pointdetermination. Where not specifically qualified in the specification,distillation temperatures are to be understood as taken at 750 mm. ofmercury. Where not specifically qualified proportions are to beunderstood as proportions by weight. In any example in which there i nonotation as to theiormation of insoluble resin, no insoluble resin wasformed.

In my companion application Serial No. 45,783, filed August 23, 1948, ofeven date herewith, I have disclosed the polymerization of mixtures ofturpentines which contain beta-pinene with the defined cyclicmono-olefine in which a vinyl group is substituted. Herein thedisclosure relates to the polymerization of a mixture of betap'inene assuch with that defined cyclic monoolefine, 1 vinyl cyclohexene 3,designated through the specification simply as vinyl cyclohexene, and tothe resin produced by that polymerization.

I claim as my invention:

1. The method of producing hard resin polymers by bringing a mixture ofl-vinyl cyclohexene-3 (cyclic dimer of butadiene) and a compoundconsisting of betapinene in a proportion of vinyl cyclohexene equal tofrom 5% to 50% the weight of the blend into reactive contact with anacid-reacting metal halide polymerization catalyst in the presence of aninert solvent diluent for the polymers of the said vinyl cyclohexene andbeta-pinene, to form hard resin polymers of vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

2. The method of producing hard resin polymers by bringing a mixture ofl-vinyl cyclohexene-3 (cyclic dimer of butadiene) and a compoundconsisting of beta-pinene in a proportion of vinyl cyclohexene equal tofrom 25% to 45% the weight of the blend into reactive contact with anacid-reacting metal halide polymerization catalyst in the presence of aninert solvent diluent for the polymers of the said vinyl cyclohexene andbeta-pinene, to form hard resin polymers of vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

3. The method of producing hard resin polymers by bringing a mixture ofl-vinyl cyclohexene-3 (cyclic dimer of butadiene) and a compoundconsisting of beta-pinene in a proportion of vinyl cyclohexene equal tofrom 5% to 50% the weight of the blend into reactive contact withaluminum chloride polymerization catalyst in the presence of an inertsolvent diluent for the polymers of the said vinyl cyclohexene andbetapinene, to form hard resin polymers of vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

4. The method of producing hard resin polymers by bringing a mixture ofl-vinyl cyclohexene-3 (cyclic dimer of butadiene) and a compoundconsisting of beta-pinene in a proportion the presence of an inertsolvent diluent for the polymers or the said vinyl cyclohexene andbetapinene to form hard resin polymers or vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

5. The method of producing hard resin polymers by bringing a mixture ofl-vinyl cyclohexene-3 (cyclic dimer of butadiene) and a compoundconsisting of beta-pinene in a proportion of vinyl cyclohexene equal tofrom 25% to 45% the weight of the blend into reactive contact withaluminum chloride polymerization catalyst in the presence of an inertsolvent diluent for the polymers of the said vinyl cyclohexene andbetapinene to form hard resin polymers of vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

6. The method of producing hard resin polymers by bringing a mixture 01l-vinyl cyclo-' hexene-3 (cyclic dimer of butadiene) and a compoundconsisting of beta-pinene in a proportion of vinyl cyclohexene equal tofrom 25% to 45% the weight 01' the blend into reactive contact withaluminum bromide polymerization catalyst in the presence of an inertsolvent diluent for the poly- 12 mers of the said vinyl cyclohexene andbetapinene to form hard resin polymers of vinyl cyclohexene andbeta-pinene in solution, and recovering the resin polymers so formed.

7. The resin produced by the process of claim 1.

SAMUEL G. BURROUGHS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,346,791 Rummelsburg Apr. 18,1944 2,349,210 Traylor May 16, 1944 2,383,084 Rummelsburg Aug. 21, 19452,401,414 Doumani June 4. 1946 2,475,234 Gleason et al. July 5, 19492,487,898 Rummelsburg Nov. 15, 1949 FOREIGN PATENTS Number Country Date614,781 Great Britain Dec. 22, 1948 OTHER REFERENCES Laitinent et 2.1.,Ind. and Eng. Chem., Analytic Ed., vol. 17, pp. 769-772, (Dec., 1945).

1. THE METHOD OF PRODUCING HARD RESIN POLYMERS BY BRINGING A MIXTURE OF1-VINYL CYCLOHEXENE-3 (CYCLIC DIMER OF BUTADINE) AND A COMPOUNDCONSISTING OF BETA-PINENE INA PROPORTION OF VINYL CYCLOHEXENE EQUAL TOFORM 5% TO 50% THE WEIGHT OF THE BLEND INTO REACTIVE CONTACT WITH ANACID-REACTING METAL HALIDE POLYMERIZATION CATALYST IN THE PRESENCE OF ANINERT SOLVENT DILUENT FOR THE POLYMERS OF THE SAID VINYL CYCLOHEXENE ANDBETA-PINENE, TO FORM HARD RESIN POLYMERS OF VINYL CYCLOHEXENE ANDBETA-PINENE IN SOLUTION, AND RECOVERING THE RESIN POLYMERS SO FORMED.